Glass Compositions and Fibers Made Therefrom

ABSTRACT

Embodiments of the present invention provides fiberizable glass compositions formed from batch compositions comprising amounts of one or more glassy minerals, including perlite and/or pumice.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part application of U.S.patent application Ser. No. 12/534,490, filed Aug. 3, 2009, which isincorporated by reference as though fully set forth herein.

FIELD OF THE INVENTION

The present invention relates to glass compositions and, in particular,to glass compositions for forming fibers.

BACKGROUND OF THE INVENTION

Large scale commercial production of continuous glass fibers (E-glassand C-glass types) comprises melting batch materials consistingprimarily of minerals that are crystalline or substantially crystallinein nature. Conversion of these crystalline raw materials to a glassystate requires significant energy to be applied during the meltingprocess. In view of the significant energy investment accompanyingcrystalline materials, glassy or amorphous minerals have sometimes beenused in the production of glass compositions. A glassy or amorphousstructure can reduce the amount of energy consumed in the meltingprocess. Glassy minerals such as basalt and obsidian, for example, havebeen used as significant portions of feedstock for the production ofmineral wool.

An associated disadvantage with some glassy minerals, however, is thehigh iron content of such minerals. Basalt and obsidian both compriserelatively large amounts of iron, thereby making their resulting meltshighly energy absorbing. As a result, use of conventional gas firedfurnaces is typically impractical for melt processing of these minerals.Electrical melting can be used to process glassy minerals of high ironcontent, but this is often a constraint in high volume glass fiberproduction as compared with conventional gas fired furnace technology.Raw materials used in the production of E-glass and C-glass fibers aregenerally low in iron, thereby permitting the use of large scale gasfired furnaces.

Perlite (and its expanded form pumice) is a mineral that naturallyoccurs in the glassy form. Perlite has not been extensively used as araw material in glass production, partially because of its compositionalparameters. The major constituents of perlite are SiO₂, Al₂O₃ and alkalioxide (R₂O). SiO₂ is typically present in perlite in an amount betweenabout 70 and about 75 weight percent. Al₂O₃ is typically present inperlite in an amount between about 12 and about 15 weight percent.Alkali oxides are typically present in perlite in an amount betweenabout 3 and about 9 weight percent. These parameters conflict with thecompositional requirements of several widely used glass compositions,including, for example, those of E-glass and C-glass.

E-glass compositions, for example, are well-suited for forming glassfibers. As a result, the majority of glass fibers used in reinforcementapplications, such as polymeric reinforcement applications, are formedfrom E-glass compositions. E-glass compositions generally limit theamount alkali oxides to no more than 2 percent. The high alkali oxidecontent of perlite is inconsistent with this limitation and rendersperlite largely unsuitable for use in batch compositions for theproduction of E-glass compositions.

Moreover, C-glass compositions have also been used to form fibersresistant to corrosion in acidic environments. In order to resist acidiccorrosion, C-glass compositions comprise a high SiO₂ content and a lowAl₂O₃ content (<8 wt. %). The high Al₂O₃ content of perlite generallyprecludes use of perlite in batch compositions for the production ofC-glass compositions.

SUMMARY

In one aspect, the present invention provides glass compositions formedfrom batch compositions comprising significant amounts of one or moreglassy minerals, including perlite and/or pumice. In another aspect, thepresent invention provides glass fibers formed from glass compositionsdescribed herein.

In one embodiment, the present invention provides a glass compositionformed from a batch composition comprising at least 10 weight percent ofa glassy mineral, at least 5 weight percent of a sodium source, whereinthe glassy mineral comprises a combination of SiO₂ and Al₂O₃ in anamount of at least 80 weight percent. In some such embodiments, thebatch composition comprises at least 25 weight percent of a glassymineral, the glassy mineral comprising a combination of SiO₂ and Al₂O₃in an amount of at least 80 weight percent. In some further suchembodiments, the batch composition comprises at least 40 weight percentof a glassy mineral, the glassy mineral comprising a combination of SiO₂and Al₂O₃ in an amount of at least 80 weight percent. In someembodiments, the glassy mineral comprising a combination of SiO₂ andAl₂O₃ is perlite, pumice or mixtures thereof.

Moreover, in some embodiments, the batch comprises at least 10 weightpercent of a sodium source. A sodium source, in some embodiments,comprises sodium carbonate (soda).

In some embodiments, the batch comprises at least 10 weight percent of asource of both silicon and aluminum. In some such embodiments, thesource of both silicon and aluminum is an aluminum-containing silicatemineral, such kaolinite, dickite, halloysite, nacrite, montmorillonite,or alkali metal aluminosilicates. In some embodiments, the batchcomprises at least 10 weight percent of a source of silicon. In someembodiments, the batch comprises at least 10 weight percent of a sourceof aluminum.

In another embodiment, the present invention provides a glasscomposition comprising 53-64 weight percent SiO₂, 8-12 weight percentAl₂O₃, 8.5-18 weight percent alkali oxide (R₂O) component and a metaloxide (RO) component, wherein the metal oxide component is present in anamount to provide a mass ratio of R₂O/RO ranging from about 0.15 toabout 1.5. In some such embodiments, the glass composition includes10-12 weight percent Al₂O₃.

In some embodiments, a R₂O component comprises Na₂O, K₂O or Li₂O ormixtures thereof. In some embodiments, a glass composition of thepresent invention comprises Na₂O in an amount ranging from 6.5 weightpercent to about 16 weight percent. A glass composition, in someembodiments, comprises K₂O in an amount ranging from 0.5 weight percentto 4 weight percent, and 2 weight percent to 4 weight percent in furtherembodiments. In some embodiments, a glass composition comprises Li₂O inan amount up to 2 weight percent.

In some embodiments, a RO component comprises MgO, CaO, SrO, BaO, or ZnOor mixtures thereof. A RO component, in some embodiments, is present ina glass composition of the present invention in an amount ranging from 7weight percent to 31 weight percent. In one embodiment, a glasscomposition comprises MgO in an amount up to about 5 weight percent. Aglass composition, in some embodiments, comprises CaO in an amountranging from 7 weight percent to 26 weight percent. In some embodiments,a glass composition comprises ZnO in an amount up to 3 weight percent.

Glass compositions of the present invention, in some embodiments,comprise metal oxides in addition to RO including, but not limited to,ZrO₂, TiO₂, MnO₂ or La₂O₃ or mixtures thereof.

In another embodiment, the present invention provides a glasscomposition comprising 56-63 weight percent SiO₂, 9-12 weight percentAl₂O₃, 12-17 weight percent RO (CaO+MgO), 12-14 weight percent R₂O(Na₂O+K₂O), 0-2 weight percent Li₂O, 0-3 weight percent ZnO, 0-3 weightpercent ZrO₂, 0-3 weight percent MnO₂ and 0-3 weight percent La₂O₃.

In another embodiment, the present invention provides a glasscomposition comprising 60-64 weight percent SiO₂, 9-12 weight percentAl₂O₃, 7-15 weight percent RO (CaO+MgO), 13-15.5 weight percent R₂O(Na₂O+K₂O), 0-2 weight percent Li₂O, 0-3 weight percent ZnO, 0-3 weightpercent ZrO₂, 0-3 weight percent MnO₂ and 0-3 weight percent La₂O₃.

In another embodiment, the present invention provides a glasscomposition comprising 55-63 weight percent SiO₂, 9-14 weight percentAl₂O₃, 11-16.5 weight percent RO (CaO+MgO), 14-17 weight percent R₂O(Na₂O+K₂O), 0-2 weight percent Li₂O, 0-3 weight percent ZnO, 0-3 weightpercent ZrO₂, 0-3 weight percent MnO₂ and 0-3 weight percent La₂O₃.

In some embodiments, glass compositions of the present invention have anFe₂O₃ content of less than 1 weight percent. Glass compositions, inother embodiments, can comprise less than 0.7 weight percent Fe₂O₃.

Glass compositions, according to some embodiments of the presentinvention are fiberizable. In some embodiments, glass compositions ofthe present invention have a forming temperature (T_(F)) ranging from1120° C. to about 1300° C. As used herein, the term “formingtemperature” means the temperature at which the glass composition has aviscosity of 1000 poise (or “log 3 temperature”). In some embodiments,glass compositions of the present invention are fiberizable at theforming temperature.

Moreover, in some embodiments, glass compositions of the presentinvention have a liquidus temperature (T_(L)) ranging from about 1020°C. to about 1240° C. In some embodiments, the difference between theforming temperature and the liquidus temperature of a glass compositionof the present invention ranges from about 45° C. to about 165° C. Insome embodiments, the difference between the forming temperature and theliquidus temperature of a glass composition of the present invention isat least 65° C.

In some embodiments, glass compositions of the present invention have amolten density at the forming temperature ranging from 2.35 g/cm³ to2.40 g/cm³. In some embodiments, glass composition of the presentinvention have molten density ranging from 2.36 g/cm³ to 2.38 g/cm³.

Glass compositions of the present invention, in some embodiments, have amolten surface tension at the forming temperature ranging from about 390E⁻³ N/m to 400 E⁻³ N/m.

As provided herein, glass fibers can be formed from some embodiments ofthe glass compositions of the present invention. In some embodiments,fibers formed from glass compositions of the present invention have amodulus (E) ranging from about 53 GPa to about 65 GPa. Moreover, in someembodiments, fibers formed from glass compositions of the presentinvention have a specific strength ranging from 1.30-1.35 E⁵ m.

Fibers formed from glass compositions of the present invention, in someembodiments, also demonstrate acidic and alkaline corrosion resistance.In one embodiment, for example, a fiber formed from a glass compositionof the present invention has a weight loss (wt. %) ranging from about0.55 to about 0.60 when exposed to 1N H₂SO₄ (pH 0) at 100° C. for onehour. In another embodiment, a fiber formed from a glass composition ofthe present invention has a weight loss (wt. %) ranging from about 0.25to 0.30 when exposed to 0.1N NaOH (pH 12) at 100° C. for one hour.

Glass fibers formed from glass compositions of the present invention canbe used in various reinforcement applications. In some embodiments,glass fibers of the present invention are used in the reinforcement ofpolymers including thermoplastics and thermosets. In some embodiments,glass fibers formed from glass compositions of the present invention areused in the reinforcement of building materials including, but notlimited to, cement and roofing systems such as shingles.

In another aspect, the present invention provides methods of makingglass compositions from batch compositions comprising significantamounts of one or more glassy minerals, including perlite and/or pumice.

In one embodiment, a method of making a glass composition of the presentinvention comprises providing a batch composition comprising at least 10weight percent of a glassy mineral and at least 5 weight percent of asodium source, the glassy mineral comprising a combination of SiO₂ andAl₂O₃ in an amount of at least 80 weight percent and heating the batchcomposition to a temperature sufficient to form the glass composition.In some embodiments, the batch comprises at least 10 weight percent ofan additional source of both silicon and aluminum. In some embodiments,the batch comprises at least 10 weight percent of an additional sourceof silicon. In some embodiments, the batch comprises at least 10 weightpercent of an additional source of aluminum. In some embodiments, thebatch composition is heated to a temperature of about 1400° C. to about1450° C.

These and other embodiments are presented in greater detail in thedetailed description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides the results of a high temperature differential thermalanalysis (DTA) comparing conversion from solid to liquid of fineparticulate perlite and a coarse particulate perlite according to oneembodiment of the present invention.

FIG. 2 illustrates an apparatus used in the determination of meltviscosities of glass compositions according to embodiments of thepresent invention.

FIG. 3 illustrates the position of the thermocouple and the number ofturns of the heating coil of a furnace used in the determination ofliquidus temperatures (T_(L)) of glass compositions according toembodiments of the present invention.

FIG. 4 provides temperature-viscosity curves for a glass compositionaccording to one embodiment of the present invention, two commerciallyavailable E-glass compositions and a C-glass composition.

FIG. 5 provides molten glass surface tensions as a function oftemperature for a glass composition according to one embodiment of thepresent invention and two commercially available E-glass compositions.

FIG. 6 is a plot of the melt or molten glass density as a function oftemperature for a glass composition according to one embodiment of thepresent invention and two commercially available E-glass compositions.

FIG. 7 is a plot electrical of conductivity as a function of temperaturefor a glass composition according to one embodiment of the presentinvention as well as E-glass and C-glass compositions.

FIG. 8 provides energy requirements for conversion of several batchcompositions to glass melt compositions according to one embodiment ofthe present invention.

FIG. 9 summarizes Weibull statistical analysis of fiber strengths ofvarious glass compositions according to some embodiments of the presentinvention.

DETAILED DESCRIPTION

Unless indicated to the contrary, the numerical parameters set forth inthe following specification are approximations that can vary dependingupon the desired properties sought to be obtained by the presentinvention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Moreover, all ranges disclosed hereinare to be understood to encompass any and all subranges subsumedtherein. For example, a stated range of “1 to 10” should be consideredto include any and all subranges between (and inclusive of) the minimumvalue of 1 and the maximum value of 10; that is, all subranges beginningwith a minimum value of 1 or more, e.g. 1 to 6.1, and ending with amaximum value of 10 or less, e.g., 5.5 to 10. Additionally, anyreference referred to as being “incorporated herein” is to be understoodas being incorporated in its entirety.

It is further noted that, as used in this specification, the singularforms “a,” “an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

Certain embodiments of the present invention can employ the variousthermodynamic and processing advantages offered by glassy minerals toprovide glass compositions having desirable properties. In one aspect,the present invention provides glass compositions formed from batchcompositions comprising significant amounts of one or more glassyminerals, including perlite and/or pumice. The glass compositions, insome embodiments, can be fiberizable glass compositions. In someembodiments, glass fibers formed from glass compositions of the presentinvention can demonstrate advantageous properties including, but notlimited to, mechanical and corrosion resistant properties equaling orexceeding glass fibers formed from previous compositions, such asE-glass and C-glass compositions.

Various embodiments of the present invention provide glass compositions,including, without limitation, fiberizable glass compositions. In oneembodiment, the present invention provides a glass composition formedfrom a batch composition comprising at least 10 weight percent of aglassy mineral and at least 5 weight percent of a sodium source, whereinthe glassy mineral comprises a combination of SiO₂ and Al₂O₃ in anamount of at least 80 weight percent. In some embodiments, the batchcomposition comprises at least 25 weight percent of a glassy mineral,the glassy mineral comprising a combination of SiO₂ and Al₂O₃ in anamount of at least 80 weight percent. In another embodiment, the batchcomposition comprises at least 40 weight percent of a glassy mineral,the glassy mineral comprising a combination of SiO₂ and Al₂O₃ in anamount of at least 80 weight percent.

In some embodiments, a glassy mineral comprising a combination of SiO₂and Al₂O₃ in an amount of at least 80 weight percent is perlite, pumiceor mixtures thereof.

Moreover, in some embodiments, the batch composition comprises at least10 weight percent of a sodium source. In another embodiment, the batchcomposition comprises at least 12 weight percent of a sodium source. Asuitable sodium source for use in batch compositions of the presentinvention, in some embodiments, comprises sodium carbonate (soda).

In some embodiments, the batch comprises at least 10 weight percent ofan additional source of both silicon and aluminum. In some suchembodiments, the source of both silicon and aluminum is analuminum-containing silicate mineral, such kaolinite, dickite,halloysite, nacrite, montmorillonite, or alkali metal aluminosilicates.In some embodiments, the batch comprises at least 10 weight percent ofan additional source of silicon. In some such embodiments, the source ofsilicon can be a silicon-containing mineral, such as silica. In someembodiments, the batch comprises at least 10 weight percent of anadditional source of aluminum. In such embodiments, the source ofaluminum can be an aluminum-containing mineral, such as corundum.

In another embodiment, the present invention provides a glasscomposition comprising 53-64 weight percent SiO₂, 8-12 weight percentAl₂O₃, 8.5-18 weight percent alkali oxide (R₂O) component and a metaloxide (RO) component, wherein the metal oxide component is present in anamount to provide a mass ratio of R₂O/RO ranging from about 0.15 toabout 1.5.

In some embodiments, a R₂O component is not limited to a single compoundbut can comprise several compounds. In some embodiments, a R₂O componentcomprises Na₂O, K₂O or Li₂O or mixtures thereof. Moreover, in someembodiments and without limitation, a R₂O component can mean Na₂O only,K₂O only, Li₂O only, a combination of Na₂O and K₂O, a combination of K₂Oand Li₂O, a combination of Na₂O and Li₂O, or a combination of Na₂O, K₂Oand Li₂O.

In some embodiments, a glass composition of the present inventioncomprises Na₂O in an amount ranging from 6.5 weight percent to about 16weight percent. In another embodiment, a glass composition comprisesNa₂O in an amount ranging from 9 weight percent to 13 weight percent. Insome embodiments, a glass composition comprises Na₂O in an amountranging from 10 weight percent to 12.5 weight percent.

In some embodiments, a glass composition of the present inventioncomprises K₂O in an amount ranging from 0.5 weight percent to 4 weightpercent. A glass composition of the present invention, in someembodiments, comprises K₂O in an amount ranging from 2 weight percent to4 weight percent. In some embodiments, a glass composition comprises K₂Oin an amount ranging from 2.5 weight percent to 3.5 weight percent.

In some embodiments, a glass composition of the present inventioncomprises Li₂O in an amount up to 2 weight percent. A glass composition,in another embodiment, comprises Li₂O in an amount ranging from 0.5weight percent to 1.5 weight percent.

In some embodiments, a RO component comprises MgO, CaO, SrO, BaO or ZnOor mixtures thereof In some embodiments, a RO component can comprise MgOonly, CaO only, SrO only, BaO only or ZnO only. In some embodiments, aRO component can comprise any combination of two or more metal oxides ofMgO, CaO, SrO, BaO and ZnO. A RO component, in some embodiments, ispresent in a glass composition of the present invention in an amountranging from 7 weight percent to 31 weight percent.

In one embodiment, a glass composition of the present inventioncomprises MgO in an amount up to 5 weight percent. A glass composition,in another embodiment, comprises MgO in an amount ranging from 1 weightpercent to 4 weight percent. In some embodiments, a glass compositioncomprises MgO in an amount ranging from 2 weight percent to 3 weightpercent.

In some embodiments, a glass composition of the present inventioncomprises CaO in an amount ranging from 7 weight percent to 26 weightpercent. A glass composition, in another embodiment, comprises CaO in anamount ranging from 8 weight percent to 20 weight percent. In someembodiments, a glass composition comprises CaO in an amount ranging from10 weight percent to 14 weight percent.

In some embodiments, a glass composition comprises ZnO in an amount upto 3 weight percent.

Glass compositions of the present invention, in some embodiments,comprise metal oxides in addition to RO including, but not limited toZrO₂, TiO₂, MnO₂ or La₂O₃ or mixtures thereof. In some embodiments, aglass composition can comprise ZrO₂ in an amount up to 3 weight percent,TiO₂ in an amount up to 3 weight percent, MnO₂ in an amount up to 3weight percent and/or La₂O₃ in an amount up to 3 weight percent.

In another embodiment, the present invention provides a glasscomposition comprising 56-63 weight percent SiO₂, 9-12 weight percentAl₂O₃, 12-17 weight percent RO (CaO+MgO), 12-14 weight percent R₂O(Na₂O+K₂O), 0-2 weight percent Li₂O, 0-3 weight percent ZnO, 0-3 weightpercent ZrO₂, 0-3 weight percent MnO₂ and 0-3 weight percent La₂O₃.

In another embodiment, the present invention provides a glasscomposition comprising 60-64 weight percent SiO₂, 9-12 weight percentAl₂O₃, 7-15 weight percent RO (CaO+MgO), 13-15.5 weight percent R₂O(Na₂O+K₂O), 0-2 weight percent Li₂O, 0-3 weight percent ZnO, 0-3 weightpercent ZrO₂, 0-3 weight percent MnO₂ and 0-3 weight percent La₂O₃.

In another embodiment, the present invention provides a glasscomposition comprising 55-63 weight percent SiO₂, 9-14 weight percentAl₂O₃, 11-16.5 weight percent RO (CaO+MgO), 14-17 weight percent R₂O(Na₂O+K₂O), 0-2 weight percent Li₂O, 0-3 weight percent ZnO, 0-3 weightpercent ZrO₂, 0-3 weight percent MnO₂ and 0-3 weight percent La₂O₃.

In some embodiments, glass compositions of the present invention have anFe₂O₃ content of less than 1 weight percent. Glass compositions, inother embodiments, can comprise less than 0.7 weight percent Fe₂O₃.

Glass compositions of the present invention, in some embodiments, have aforming temperature (T_(F)) ranging from about 1120° C. to about 1300°C. In another embodiment, glass compositions of the present inventionhave a forming temperature ranging from about 1150° C. to about 1250° C.In some embodiments, glass compositions have a forming temperatureranging from about 1200° C. to about 1225° C.

Glass compositions of the present invention, in some embodiments, have aliquidus temperature ranging from about 1020° C. to about 1240° C. Inanother embodiment, glass compositions of the present invention have aliquidus temperature ranging from about 1070° C. to about 1200° C. Insome embodiments, glass compositions of the present invention have aliquidus temperature ranging from about 1110° C. to about 1140° C.

In some embodiments, the difference between the forming temperature andthe liquidus temperature of a glass composition of the present inventionranges from about 45° C. to about 165° C. In some embodiments, thedifference between the forming temperature and the liquidus temperatureof a glass composition of the present invention is at least 65° C.

In some embodiments, glass compositions of the present invention have amolten density at the forming temperature ranging from 2.35 g/cm³ to2.40 g/cm³. In some embodiments, glass compositions of the presentinvention have molten density ranging from 2.36 g/cm³ to 2.38 g/cm³. Asdiscussed further herein, in some embodiments, molten densities of someglass compositions of the present invention are 5% to 7% lower than themolten densities of some E-glass compositions. As a result, glass fibersformed from some glass compositions of the present invention are lighterper unit volume in comparison to some E-glass fibers. Lighter glassfibers can be advantageous in many applications, particularly materialreinforcement applications, such as polymeric reinforcementapplications, where weight savings are often highly desirable. Moreover,as a result of lower densities, glass fibers formed from some glasscompositions of the present invention can have larger diameters incomparison to some E-glass fibers of the same weight, thereby providingenhanced mechanical properties.

Additionally, glass compositions of the present invention, in someembodiments, have a molten surface tension at the forming temperatureranging from about 390 E⁻³ N/m to 400 E⁻³ N/m.

As provided herein, glass compositions of the present invention can beproduced from batch compositions comprising a significant amount of oneor more glassy minerals, including perlite and/or pumice. In beingproduced from batch compositions comprising a significant amount ofglassy minerals, glass compositions of the present invention can realizesizable energy savings in some embodiments. As discussed further herein,in some embodiments, production of a melt of a glass composition of thepresent invention requires up to 33% less energy in comparison to thatrequired to produce a melt of some E-glass compositions.

Glass compositions of the present invention can be produced by severalmethods. In one embodiment, a method of producing a glass compositioncomprises providing a batch composition comprising at least 10 weightpercent of a glassy mineral and at least 5 weight percent of a sodiumsource, the glassy mineral comprising a combination of SiO₂ and Al₂O₃ inan amount of at least 80 weight percent and heating the batchcomposition to a temperature sufficient to form a melt of the glasscomposition. In some embodiments, the batch composition is heated to atemperature of about 1400° C. to about 1450° C. In some embodiments, thebatch comprises at least 10 weight percent of an additional source ofboth silicon and aluminum. In some such embodiments, the source of bothsilicon and aluminum is an aluminum-containing silicate mineral, suchkaolinite, dickite, halloysite, nacrite, montmorillonite, or alkalimetal aluminosilicates. In some embodiments, the batch comprises atleast 10 weight percent of an additional source of silicon. In someembodiments, the batch comprises at least 10 weight percent of anadditional source of aluminum.

In some embodiments, the batch composition comprises at least 25 weightpercent of a glassy mineral, the glassy mineral comprising a combinationof SiO₂ and Al₂O₃ in an amount of at least 80 weight percent. In anotherembodiment, the batch composition comprises at least 40 weight percentof a glassy mineral, the glassy mineral comprising a combination of SiO₂and Al₂O₃ in an amount of at least 80 weight percent.

In some embodiments, a glassy mineral comprising a combination of SiO₂and Al₂O₃ in an amount of at least 80 weight percent is perlite, pumiceor mixtures thereof. Perlite and/or pumice used in the production ofglass compositions of the present invention, in some embodiments, isprovided in particulate or powder form. In some embodiments, additionalenergy savings can be realized by using perlite and/or pumicecompositions having fine particle size as opposed to coarser particlesizes. FIG. 1 illustrates the results of a high temperature differentialthermal analysis (DTA) comparing the conversion from solid to liquid ofa fine particulate perlite (about 200 mesh) and a coarse particulateperlite (about 45 mesh). As illustrated in FIG. 1, the fine particulateperlite requires less energy during conversion from solid to liquid incomparison to the coarse particulate perlite, although both the fine andthe coarse particulate perlite are glassy or amorphous at roomtemperature. Moreover, the fine particulate perlite begins liquidformation at a lower temperature than the coarse particulate perlite.

Moreover, in some embodiments, batch compositions of the presentinvention comprise at least 10 weight percent of a sodium source. Insome embodiments, batch compositions comprise at least 12 weight percentof a sodium source. A suitable sodium source for use in batchcompositions of the present invention, in some embodiments, comprisessodium carbonate (soda).

In some embodiments, batch compositions used to produce glasscompositions of the present invention further comprise other mineralsincluding, but not limited to, limestone, dolomite or mixtures thereof.In one embodiment, for example, a batch composition further comprises upto 17 weight percent limestone. In another embodiment, a batchcomposition further comprises up to 13 weight percent dolomite.

As provided herein, glass fibers can be formed from any of the glasscompositions of the present invention. Glass fibers according to thevarious embodiments of the present invention can be formed using anyprocess known in the art for forming glass fibers, and more desirably,any process known in the art for forming essentially continuous glassfibers. For example, although not limiting herein, the glass fibersaccording to non-limiting embodiments of the present invention can beformed using direct-melt or indirect-melt fiber forming methods. Thesemethods are well known in the art and further discussion thereof is notbelieved to be necessary in view of the present disclosure. See, e.g.,K. L. Loewenstein, The Manufacturing Technology of Continuous GlassFibers, 3^(rd) Ed., Elsevier, N.Y., 1993 at pages 47-48 and 117-234.

In one embodiment, the present invention provides a glass fibercomprising a glass composition formed from a batch compositioncomprising at least 10 weight percent of a glassy mineral and at least 5weight percent of a sodium source, wherein the glassy mineral comprisesa combination of SiO₂ and Al₂O₃ in an amount of at least 80 weightpercent. In some embodiments, the batch composition comprises at least25 weight percent of a glassy mineral, the glassy mineral comprising acombination of SiO₂ and Al₂O₃ in an amount of at least 80 weightpercent. In another embodiment, the batch composition comprises at least40 weight percent of a glassy mineral, the glassy mineral comprising acombination of SiO₂ and Al₂O₃ in an amount of at least 80 weightpercent. In some embodiments, the batch composition comprises at least10 weight percent of a source of both silicon and aluminum. In someembodiments, the batch comprises at least 10 weight percent of a sourceof silicon. In some embodiments, the batch comprises at least 10 weightpercent of a source of aluminum.

In another embodiment, the present invention provides a glass fibercomprising 53-64 weight percent SiO₂, 8-12 weight percent Al₂O₃, 8.5-18weight percent alkali oxide (R₂O) component and a metal oxide (RO)component, wherein the metal oxide component is present in an amount toprovide a mass ratio of R₂O/RO ranging from about 0.15 to about 1.5. Insome such embodiments, the glass composition includes 10-12 weightpercent Al₂O₃.

In another embodiment, the present invention provides a glass fibercomprising 56-63 weight percent SiO₂, 9-12 weight percent Al₂O₃, 12-17weight percent RO (CaO+MgO), 12-14 weight percent R₂O (Na₂O+K₂O), 0-2weight percent Li₂O, 0-3 weight percent ZnO, 0-3 weight percent ZrO₂,0-3 weight percent MnO₂ and 0-3 weight percent La₂O₃.

In another embodiment, the present invention provides a glass fibercomprising 60-64 weight percent SiO₂, 9-12 weight percent Al₂O₃, 7-15weight percent RO (CaO+MgO), 13-15.5 weight percent R₂O (Na₂O+K₂O)), 0-2weight percent Li₂O, 0-3 weight percent ZnO, 0-3 weight percent ZrO₂,0-3 weight percent MnO₂ and 0-3 weight percent La₂O₃.

In another embodiment, the present invention provides a glass fibercomprising 55-63 weight percent SiO₂, 9-14 weight percent Al₂O₃, 11-16.5weight percent RO (CaO+MgO), 14-17 weight percent R₂O (Na₂O+K₂O), 0-2weight percent Li₂O, 0-3 weight percent ZnO, 0-3 weight percent ZrO₂,0-3 weight percent MnO₂ and 0-3 weight percent La₂O₃.

In some embodiments, fibers formed from glass compositions of thepresent invention have a modulus (E) ranging from about 53.0 GPa toabout 65.0 GPa. In another embodiment, fibers formed form glasscompositions of the present invention have a modulus (E) ranging fromabout 56 GPa to about 62 GPa. Moreover, in some embodiments, fibersformed from glass compositions of the present invention have a specificstrength ranging from 1.30-1.35 E⁵ m. Fibers formed from glasscompositions of the present invention, in some embodiments, alsodemonstrate acidic and alkaline corrosion resistance. In one embodiment,for example, a glass fiber formed from a glass composition of thepresent invention has a weight loss (wt. %) ranging from 0.55 to 0.60when exposed to 1N H₂SO₄ (pH 0) at 100° C. for one hour. In anotherembodiment, a glass fiber formed from a glass composition of the presentinvention has a weight loss (wt. %) ranging from 0.60 to 1.70 whenexposed to 1N H₂SO₄ (pH 0) at 100° C. for one hour.

In another embodiment, a fiber formed from a glass composition of thepresent invention has a weight loss (wt. %) ranging from about 0.25 toabout 0.30 when exposed to 0.1N NaOH (pH 12) at 100° C. for one hour. Afiber formed from a glass composition of the present invention, in someembodiments, has a weight loss (wt. %) ranging from 0.35 to 0.85 whenexposed to 0.1N NaOH (pH 12) at 100° C. for one hour.

Although not limiting herein, glass fibers according to some embodimentsof the present invention can be useful in structural reinforcementapplications. In some embodiments, glass fibers of the present inventionare used in the reinforcement of polymers including thermoplastics andthermosets. In some embodiments, glass fibers formed from glasscompositions of the present invention are used in the reinforcement ofbuilding materials including, but not limited to, cement and roofingsystems such as shingles.

In one embodiment, the present invention provides a polymeric compositecomprising a polymeric material and at least one glass fiber in thepolymeric material, the at least one glass fiber comprising a glasscomposition a formed from a batch composition comprising at least 10weight percent of a glassy mineral and at least 5 weight percent of asodium source, wherein the glassy mineral comprises a combination ofSiO₂ and Al₂O₃ in an amount of at least 80 weight percent. In someembodiments, the batch composition comprises at least 25 weight percentof a glassy mineral, the glassy mineral comprising a combination of SiO₂and Al₂O₃ in an amount of at least 80 weight percent. In anotherembodiment, the batch composition comprises at least 40 weight percentof a glassy mineral, the glassy mineral comprising a combination of SiO₂and

Al₂O₃ in an amount of at least 80 weight percent.

In another embodiment, the present invention provides a polymericcomposite comprising a polymeric material and at least one glass fiberin the polymeric material, the at least one glass fiber comprising 53-64weight percent SiO₂, 8-12 weight percent Al₂O₃, 8.5-18 weight percentalkali oxide (R₂O) component and a metal oxide (RO) component, whereinthe metal oxide component is present in an amount to provide a massratio of R₂O/RO ranging from about 0.15 to about 1.5. In some suchembodiments, the glass composition includes 10-12 weight percent Al₂O₃.

In another embodiment, the present invention provides a polymericcomposite comprising a polymeric material and at least one glass fiberin the polymeric material, the at least one glass fiber comprising 56-63weight percent SiO₂, 9-12 weight percent Al₂O₃, 12-17 weight percent RO(CaO+MgO), 12-14 weight percent R₂O (Na₂O+K₂O), 0-2 weight percent Li₂O,0-3 weight percent ZnO, 0-3 weight percent ZrO₂, 0-3 weight percent MnO₂and 0-3 weight percent La₂O₃.

In another embodiment, the present invention provides a polymericcomposite comprising a polymeric material and at least one glass fiberin the polymeric material, the at least one glass fiber comprising 60-64weight percent SiO₂, 9-12 weight percent Al₂O₃, 7-15 weight percent RO(CaO+MgO), 13-15.5 weight percent R₂O (Na₂O+K₂O)), 0-2 weight percentLi₂O, 0-3 weight percent ZnO, 0-3 weight percent ZrO₂, 0-3 weightpercent MnO₂ and 0-3 weight percent La₂O₃.

In another embodiment, the present invention provides a polymericcomposite comprising a polymeric material and at least one glass fiberin the polymeric material, the at least one glass fiber comprising 55-63weight percent SiO₂, 9-14 weight percent Al₂O₃, 11-16.5 weight percentRO (CaO+MgO), 14-17 weight percent R₂O (Na₂O+K₂O), 0-2 weight percentLi₂O, 0-3 weight percent ZnO, 0-3 weight percent ZrO₂, 0-3 weightpercent MnO₂ and 0-3 weight percent La₂O₃.

Polymeric composites according to the various embodiments of the presentinvention can be made by any method known in the art for makingpolymeric composites. For example, in one embodiment, polymericcomposites according to the present invention can be made byimpregnating woven fabrics or non-woven fabrics or mats of glass fiberswith a polymeric material and then curing the polymeric material. Inanother embodiment, continuous glass fibers and/or chopped glass fiberscomprising glass compositions of the present invention can be disposedin the polymeric material. Depending on the identity of the polymericmaterial, the polymeric material can be cured subsequent to receivingthe continuous or chopped glass fibers.

Various non-limiting embodiments of the present invention will now beillustrated in the following, non-limiting examples.

Examples 1 through 6 of glass compositions of the present inventionprovided in Table I were prepared by providing mixtures of ingredientscovering 65-72 weight percent perlite, 0-22 weight percent dolomite,6-35 weight percent limestone and 0-8 weight percent soda. The specificamounts of perlite, dolomite, limestone and/or soda used to produceExamples 1 through 6 were determined by reference to the compositionalparameters of each mineral in relation to the desired compositionalparameters of each glass composition. Mixtures of the minerals weresubsequently heated to a temperature of about 1400° C. to obtain moltenglass compositions. The molten glass compositions were cooled to provideglass compositions of Examples 1 through 6.

TABLE I Glass Compositions Ex. SiO₂ Al₂O₃ CaO MgO Na₂O K₂O R₂O Fe₂O₃TiO₂ SO₃ F M_(x)O_(y) 1 59.29 10.84 20.37 3.00 2.82 3.06 5.88 0.48 0.140.00 0.00 0.00 2 59.29 10.84 19.37 4.00 2.82 3.06 5.88 0.48 0.14 0.000.00 0.00 3 59.29 10.84 18.87 4.50 2.82 3.06 5.88 0.48 0.14 0.00 0.000.00 4 59.29 10.84 18.37 5.00 2.82 3.06 5.88 0.48 0.14 0.00 0.00 0.00 554.41 9.95 25.68 4.00 2.76 2.59 5.38 0.47 0.14 0.00 0.00 0.00 6 59.2910.84 23.37 0.00 2.82 3.06 5.88 0.48 0.14 0.00 0.00 0.00

Examples 7 through 13 of glass compositions of the present inventionprovided in Table II were prepared by providing mixtures of ingredientscovering 69-71 weight percent perlite, 6-20 weight percent limestone and7-10 weight percent soda. The specific amounts of perlite, limestone andsoda used to produce Examples 7 through 13 were determined by referenceto the compositional parameters of each mineral in relation to thedesired compositional parameters of each glass composition. Mixtures ofthe minerals were subsequently heated to a temperature of about 1400° C.to obtain molten glass compositions. The molten glass compositions werecooled to provide glass compositions of Examples 7 through 13.

TABLE II Glass Compositions Ex. SiO₂ Al₂O₃ CaO MgO Na₂O K₂O R₂O Fe₂O₃TiO₂ SO₃ F M_(x)O_(y) 7 62.66 11.46 9.28 2.98 9.20 3.23 12.43 0.51 0.140.25 0.30 0.00 8 61.11 11.17 14.03 0.00 9.29 3.15 12.42 0.49 0.14 0.320.30 0.00 9 62.61 11.45 11.26 0.00 10.19 3.23 13.42 0.51 0.14 0.32 0.300.00 10 61.13 11.17 13.04 0.00 10.19 3.23 13.42 0.49 0.14 0.32 0.30 0.0011 58.93 10.76 12.57 0.00 10.34 2.60 13.22 0.47 3.00 0.09 0.28 0.95* 1258.93 10.76 12.57 0.00 10.34 2.60 13.22 0.47 1.08 0.09 0.28 2.87* 1357.47 10.78 9.12 0.00 10.44 3.05 13.49 0.62 0.15 0.09 0.28 8.00* *ZrO₂and TiO₂ were added to the batch composition used to produce the glasscomposition.

Examples 14 through 19 of glass compositions of the present inventionprovided in Table III were prepared by providing mixtures of ingredientscovering 69-72 weight percent perlite, 0-13 weight percent dolomite,3-17 weight percent limestone and 7-10 weight percent soda. The specificamounts of perlite, limestone, soda and/or dolomite used to produceExamples 14 through 19 were determined by reference to the compositionalparameters of each mineral in relation to the desired compositionalparameters of each glass composition. Mixtures of the minerals weresubsequently heated to a temperature of about 1400° C. to obtain moltenglass compositions. The molten glass compositions were cooled to provideglass compositions of Examples 14 through 19.

TABLE III Glass Compositions Ex. SiO₂ Al₂O₃ CaO MgO Na₂O K₂O R₂O Fe₂O₃TiO₂ SO₃ F M_(x)O_(y) 14 62.62 11.45 10.77 0.00 10.69 3.23 13.92 0.510.14 0.30 0.30 0.00 15 61.91 11.38 7.99 3.00 11.21 3.27 14.48^(#) 0.600.14 0.20 0.00 1.0^(#)/0.30* 16 63.65 11.93 4.39 2.56 13.04 3.37 16.410.70 0.17 0.20 0.00 0.00 17 61.14 11.17 12.05 0.00 11.26 3.15 14.41 0.490.14 0.30 0.30 0.00 18 61.65 11.29 10.94 0.00 11.73 3.18 14.92 0.52 0.140.25 0.30 0.00 19 61.65 11.29 7.96 2.98 11.73 3.18 14.92 0.52 0.14 0.300.25 0.00 ^(#)1 wt % Li₂O replaced 1 wt % Na₂O; Sb₂O₃ used in refiningremoved *Sb₂O₃ used for refining

Examples 20 through 37 of glass compositions of the invention providedin Table IV were prepared by providing mixtures of ingredients covering68-73 weight percent perlite, 0-13 weight percent dolomite, 4-16 weightpercent limestone and 12-17 weight percent soda. The specific amounts ofperlite, limestone, soda and/or dolomite used to produce Examples 20through 37 were determined by reference to the compositional parametersof each mineral in relation to the desired compositional parameters ofeach glass composition. Mixtures of the minerals were subsequentlyheated to a temperature of about 1400° C. to obtain molten glasscompositions. The molten glass compositions were cooled to provide glasscompositions of Examples 20 through 37.

TABLE IV Glass Compositions Ex. SiO₂ Al₂O₃ CaO MgO Na₂O K₂O R₂O Fe₂O₃TiO₂ SO₃ F M_(x)O_(y) 20 61.14 11.17 11.05 0.00 12.26 3.15 15.41 0.490.14 0.30 0.30 0.00 21 60.78 11.10 11.65 0.00 12.31 3.13 15.44 0.50 0.140.20 0.20 0.00 22 60.74 11.09 8.65 2.99 12.31 3.13 15.44 0.50 0.14 0.200.25 0.00 23 61.01 10.77 8.25 2.97 12.30 3.91 16.20 0.58 0.07 0.02 0.120.00 24 60.64 10.71 8.80 2.96 12.22 3.88 16.10 0.58 0.07 0.02 0.12 0.0025 60.94 10.76 8.79 2.54 12.28 3.90 16.18 0.58 0.07 0.02 0.12 0.00 2660.22 10.63 9.15 2.52 10.54 3.86 14.40 2.88 0.07 0.02 0.11 0.00 27 60.9210.76 8.24 2.97 12.28 3.90 16.18 0.58 0.07 0.18 0.12 0.00 28 60.55 10.698.78 2.96 12.20 3.88 16.08 0.58 0.07 0.18 0.12 0.00 29 60.84 10.74 8.772.54 12.26 3.90 16.15 0.58 0.07 0.18 0.12 0.00 30 60.12 10.62 9.13 2.5110.53 3.85 14.38 2.88 0.07 0.17 0.11 0.00 31 55.33 9.77 12.86 5.38 4.593.54 8.13 0.54 0.06 0.07 0.11 7.75* 32 58.03 10.25 13.49 5.64 4.81 3.718.53 0.56 0.07 0.07 0.11 3.25* 33 55.59 9.82 6.17 3.06 10.03 3.56 13.590.53 0.06 0.07 0.11 11.01** 34 62.34 14.32 11.20 0.38 9.04 2.17 11.210.34 0.04 0.11 0.06 0.00 35 62.87 11.50 7.98 0.00 13.25 3.24 16.50 0.510.14 0.30 0.20 0.00 36 61.14 11.17 10.06 0.00 13.25 3.15 16.40 0.49 0.140.30 0.30 0.00 37 60.25 11.01 9.00 1.98 12.70 3.54 16.24 0.81 0.03 0.120.00 0.00 *B₂O₃ used as additives **ZnO used to replace 1 wt % Na₂O and1 wt % CaO plus Sb₂O₃ removal

The glass composition of Example 38 provided in Table V was prepared inaccordance with the glass composition of Example 12 above, except 1 wt %Li₂O was used to replace 1 wt % Na₂O and any Sb₂O₃ used during refiningwas removed. The glass composition of Example 39 in Table V was preparedin accordance with the glass composition of Example 12 above, except ZnOwas used to replace 1 wt % Na₂O and 1 wt % CaO and any Sb₂O₃ used duringrefining was removed.

TABLE V Glass Compositions Ex. SiO₂ Al₂O₃ CaO MgO Na₂O K₂O R₂O Fe₂O₃TiO₂ SO₃ F M_(x)O_(y) 38 61.93 11.34 7.99 3.00 10.29 3.20 13.49 0.520.14 0.30 0.30 1.00 39 61.93 11.34 6.99 3.00 10.29 3.20 13.49 0.52 0.140.30 0.30 2.00

Examples 40 through 71 of glass compositions of the present inventionprovided in Table VI were prepared in accordance with the glasscomposition of Example 12 above, except the glass compositions weredesigned to include various combinations of Li₂O, La₂O₃, MnO₂, TiO₂, ZnOand ZrO₂. Various amounts of Li₂CO₃, La₂O₃, MnO₂, TiO₂, ZnO and ZrO₂were incorporated into the batch composition of Example 12 to produceExamples 39-70. Moreover, each of the glass compositions of Examples39-70 also included 0.09 wt % SO₃, 0.27-0.28 wt % F and 0.53-0.55 wt %Fe₂O₃.

TABLE VI Glass Compositions Ex. SiO₂ Al₂O₃ CaO MgO Na₂O K₂O R₂O Li₂O ZnOZrO₂ TiO₂ La₂O₃ MnO₂ 40 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 0.910.91 2.74 0.91 2.74 41 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 2.740.91 2.74 0.91 0.91 42 57.22 10.52 7.38 2.77 10.33 3.01 13.34 1.38 0.922.77 0.92 0.92 0.92 43 54.70 10.06 7.06 2.65 9.87 2.87 12.75 0.44 2.650.88 2.65 2.65 2.65 44 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 2.670.89 0.89 2.67 2.67 45 53.29 9.80 6.88 2.58 9.62 2.80 12.42 1.29 2.582.58 2.58 2.58 2.58 46 54.70 10.06 7.06 2.65 9.87 2.87 12.75 0.44 2.652.65 2.65 0.88 2.65 47 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 0.892.67 2.67 0.89 2.67 48 58.85 10.82 7.59 2.85 10.62 3.09 13.72 0.47 0.950.95 0.95 0.95 0.95 49 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 0.912.74 0.91 2.74 0.91 50 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 2.740.91 0.91 2.74 0.91 51 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 2.670.89 2.67 2.67 0.89 52 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 2.672.67 0.89 2.67 0.89 53 54.70 10.06 7.06 2.65 9.87 2.87 12.75 0.44 2.652.65 0.88 2.65 2.65 54 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 0.910.91 2.74 2.74 0.91 55 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 0.890.89 2.67 2.67 2.67 56 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 0.892.67 2.67 2.67 0.89 57 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 0.912.74 0.91 0.91 2.74 58 57.22 10.52 7.38 2.77 10.33 3.01 13.34 1.38 2.770.92 0.92 0.92 0.92 59 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 2.670.89 2.67 0.89 2.67 60 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 0.910.91 0.91 2.74 2.74 61 57.22 10.52 7.38 2.77 10.33 3.01 13.34 1.38 0.920.92 2.77 0.92 0.92 62 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 2.672.67 2.67 0.89 0.89 63 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 2.742.74 0.91 0.91 0.91 64 54.70 10.06 7.06 2.65 9.87 2.87 12.75 0.44 0.882.65 2.65 2.65 2.65 65 57.22 10.52 7.38 2.77 10.33 3.01 13.34 1.38 0.920.92 0.92 0.92 2.77 66 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 0.892.67 0.89 2.67 2.67 67 54.70 10.06 7.06 2.65 9.87 2.87 12.75 0.44 2.652.65 2.65 2.65 0.88 68 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 2.740.91 0.91 0.91 2.74 69 55.18 10.15 7.12 2.67 9.96 2.90 12.86 1.34 2.672.67 0.89 0.89 2.67 70 57.22 10.52 7.38 2.77 10.33 3.01 13.34 1.38 0.920.92 0.92 2.77 0.92 71 56.70 10.43 7.32 2.74 10.23 2.98 13.21 0.46 0.912.74 2.74 0.91 0.91

Examples 72 through 74 of glass compositions of the present inventionprovided in Table VII may be prepared by providing mixtures ofingredients covering 11-41 weight percent perlite, 0-55 weight percentdolomite, 12-17 weight percent limestone, 0-30 weight percent alkalialuminosilicate mineral, 34-56 weight percent silica, 0-19 weightpercent clay (kaolinite), and 1-3 weight percent rouge. The specificamounts of perlite, dolomite, alkali aluminosilicate mineral, silica,clay and/or rouge used to produce Examples 72 through 74 were determinedby reference to the compositional parameters of each mineral in relationto the desired compositional parameters of each glass composition.Mixtures of the minerals are heated to a temperature of about 1400° C.to obtain molten glass compositions. The molten glass compositions arecooled to provide glass compositions of Examples 72 through 74.

TABLE VII Glass Compositions Ex. SiO₂ Al₂O₃ CaO MgO Na₂O K₂O TiO2 Fe₂O₃72 61.60 10.64 11.27 0.56 13.10 2.38 0.01 0.44 73 61.56 10.68 11.08 0.5913.58 2.08 0.02 0.42 74 62.44 10.70 10.51 1.76 12.91 0.70 0.37 0.61

I. Melt Properties

The melt properties of several glass compositions of Examples 1 through71 were investigated. Investigation of the melt properties of glasscompositions of the present invention assisted in the determination ofhow various compositional parameters affect processing considerationsincluding forming temperatures (T_(F)) and liquidus (T_(L)) temperaturesof the glass compositions.

The measurement of melt viscosity for determining forming temperaturesof various glass compositions of the present invention was done by thecounter-balance method over the viscosity range of 10²-10⁵ Poise. Theapparatus used to execute the method was calibrated using NIST standardglass. FIG. 2 shows schematics of the apparatus.

The apparatus (1) for measuring melt viscosity comprised a platinum ball(2) with a diameter of 16 mm. The platinum ball (2) was hung on a thinplatinum wire (6) with the help of a special bracket/holder (11)attached to the right scale of the analytical balance. Initially, thefirst the end of the platinum wire (6) was attached to thebracket/holder at point A. After warming the furnace (9), the platinumball was placed in the sample melt inside the crucible (3) and the firstend of the wire was attached to the bracket/holder at point B to locatethe platinum ball (2) in the center of the melt. The distance betweenthe platinum ball (2) and the walls of the crucible (3) was 13-15 mm. Ifthe distance were smaller, it would affect the precision of themeasurement.

The movement of the platinum ball (3) in the melt was performed bychanging the weight of the rider. The speed of the movement of the ballin the melt was defined in relative numbers of the balance indicatorshift that was observed on the balance scale. When the balance indicatormoved 100 points to both sides from zero position, the ball in the meltshifted 1.7 mm from the central position up and down. The sensitivity ofthe balance was 10 mg per 100 points. A Pt/PtRh thermocouple was placedin the furnace next to the crucible (3) and provided automatictemperature control of the furnace. The hot end of another thermocouple(5) was inside the crucible (10) filled with Al₂O₃ powder. Thisthermocouple was connected with the potentiometer to control the furnacetemperature at the set point. The temperature control had a precision±1.5° C.

During the testing, the platinum ball (2) moved from a marked upperposition in the melt to a lower marked position under its gravity, thetime of which was recorded using a stopwatch with the precision within0.1 second. The time of the balance scale shift to 20-60 scale divisionswas measured depending on the viscosity of the melt. The speed of theplatinum ball (2) movement (per scale division/seconds) was taken as anaverage value of six measurements.

Using the velocity (V)-weight (G) data, a plot of V-G was constructedfor each glass composition under investigation, all of which showedstraight lines passing through the point of origin of the V-Gcoordinates. The slope k of each line was correlated with melt viscosityin a form of:

log η=a*log(tgk)+b

where a (1.09) and b (0.87) were constants determined from cellcalibration using a NIST standard glass (710A). The relative error indefining viscosity was within 3% over the viscosity range, 2.5<logη<3.5, and within 4-6% over the range, log η<2.5 and log η>3.5.

The measurement of glass composition liquidus temperature (T_(L)) wasconducted in a tube type gradient furnace with maximum temperature 1250°C. The furnace chamber had a dimension of 480 mm in length and 50 mm indiameter. The geometry and dimension of the furnace were close to thoserecommended by the ASTM C829-81. FIG. 3 illustrates the position of thethermocouple and the number of turns of the heating coil. The coil wasmade of NiCr resistance alloy wires with diameter of 2 mm.

Table VIII summarizes measured liquidus temperature (T_(L)) andreference temperature of forming (T_(F)) defined by melt viscosity of1000 Poise for glass compositions of Examples 1-22. Glass compositionsof Examples 1-6 demonstrated liquidus temperatures greater than 1240°C., the upper limit of the gradient temperature furnace setting. As aresult, no viscosity measurements were made for these compositions for adetermination of forming temperature. Moreover, several glasscompositions displayed desirable melt properties by having lowerliquidus and forming temperatures while maintaining a difference inliquidus temperature and forming temperature of at least 65° C. Examples18, 20 and 21 each provided a forming temperature under 1222° C. whilemaintaining a difference in liquidus and forming temperature of at least75° C.

TABLE VIII Melt Properties of Glass Compositions T_(L) T_(F) Delta T(T_(F) − T_(L)) Example (° C.) (° C.) (° C.) 1 1235 1226 −9 2 >12403 >1240 4 >1240 5 >1240 6 >1240 7 1296 8 1190 1265 75 9 1290 10 11851246 61 11 1190 1236 46 12 1130 1265 135 13 1185 1224 39 14 1155 1248 9315 1085 1250 165 16 1170 1225 55 17 1180 1204 24 18 1135 1222 87 19 10901252 162 20 1140 1220 80 21 1130 1205 75 22 1120 1262 142

Table IX summarizes measured liquidus temperature (T_(L)) and theforming (T_(F)) temperature for glass compositions of Examples 40through 71 as a function of weight percent of Li₂O in the glasscompositions. As provided in Table IX, Li₂O plays a significant role inlowering the liquidus and forming temperatures of glass compositions ofthe present invention with minimum reductions in forming and liquidustemperatures being 30° C. and 43° C. respectively.

TABLE IX Melt Properties of Glass Compositions High Li₂O (1.5 wt %) LowLi₂O (0.5 wt %) Delta Delta EX. T_(F) ° C. T_(L) ° C. T ° C. EX. T_(F) °C. T_(L) ° C. T ° C. 42 1148 1060 88 40 1187 1100 87 44 1156 1054 102 411176 1073 103 45 1157 1065 92 43 1165 1083 82 47 1145 1058 87 46 11791081 98 51 1142 1067 82 48 1210 1096 114 52 1158 1054 104 49 1210 1098112 55 1154 1031 123 50 1206 1086 120 56 1160 1024 136 53 1193 1084 10958 1164 1062 102 54 1205 1090 115 59 1124 1054 70 57 1222 1074 148 611160 1054 106 60 1204 1087 117 62 1148 1043 105 63 1215 1068 147 65 11631065 98 64 1192 1073 119 66 1162 1057 105 67 1190 1073 117 69 1154 106094 68 1190 1087 103 70 1158 1060 98 71 1208 1073 135

FIG. 4 provides temperature-viscosity curves for the glass compositionof Example 18, two E-glass compositions and a C-glass composition. FromFIG. 4, it is noted that the temperature-viscosity characteristics ofthe glass composition of Example 18 are similar to those of the C-glasscomposition. Moreover, the viscosity change for the glass composition ofExample 18 is not as steep as that provided for the E-glasscompositions. As a result, the glass composition of claim 18 can becharacterized as a “long” glass whereas the E-glass compositions are“short” glasses. Longer glasses, such as Example 18, in principle, favorfine filament production forming due to less forming tension as a resultof slower reduction in melt viscosity over the forming temperature rangeright after fiber exit from the forming tip.

FIG. 5 further illustrates the reduction in forming tension by providingmolten glass surface tensions as a function of temperature for the glasscomposition of Example 22 in comparison two E-glass compositions. Asprovided in FIG. 5, the glass composition of Example 22 at the formingtemperature has 9% and 14% lower surface tension than the E-glasscompositions.

FIG. 6 is a plot of the melt or molten glass density as a function oftemperature for the glass composition of Example 22 in comparison withtwo E-glass compositions. As provided in FIG. 6, the glass compositionof Example 22 demonstrated a temperature dependency (slope) similar tothe E-glass compositions but had a molten density 5% and 7% lower thanthe E-glass compositions respectively. As a result, glass fibers formedfrom some glass compositions of the present invention are lighter perunit volume in comparison to some E-glass fibers. Lighter glass fiberscan be advantageous in many applications, particularly materialreinforcement application, such as polymeric reinforcement applications,where weight savings are highly desirable. Moreover, as a result oflower densities, glass fibers formed from some glass compositions of thepresent invention can have larger diameters in comparison to someE-glass fibers of the same weight, thereby providing enhanced mechanicalproperties.

FIG. 7 is a plot electrical of conductivity as a function of temperaturefor the glass composition of Example 25 in comparison with E-glass andC-glass compositions. As provided in FIG. 7, the glass composition ofExample 25 and the C-glass composition display much higher electricalconductivities than the E-glass due to their significantly higher alkalimetal content. The melt conductivity of an inorganic glass compositionis generally dominated by the mobile ions of sodium and potassium. As aresult of low sodium and potassium ion content in E-glass compositions,electrical melting technology is only used as a secondary boost systemfor E-glass processing. However, electrical melting technology has beenused as a primary energy for the processing of C-glass compositions.Given that glass compositions of the present invention, in someembodiments, demonstrate higher melt conductivities than some C-glasscompositions, electrical melting technology may find application toprocessing glass compositions of the present invention.

Additionally, glass compositions of the present invention formed frombatch compositions comprising perlite and/or pumice, in someembodiments, require less energy for converting the batch composition toa glass melt composition. FIG. 8 provides the energy required to convertthe batch composition comprising perlite to the glass melt compositionof Example 12. FIG. 8 also provides the energy required to convert anE-glass batch composition to the associated glass melt. As shown in FIG.8, the energy required to convert the batch composition of Example 12into a glass melt composition was 20% less than the energy required toconvert the E-glass batch composition to glass melt composition. Theenergy required to convert a second E-glass batch composition to a glassmelt composition was also compared with the energy required to convertthe batch composition of Example 12 into a glass melt composition. Theenergy required to convert the batch composition of Example 12 was about33% percent lower than the energy to convert the second E-glass batchcomposition to a glass melt composition.

II. Acid and Alkaline Corrosion Resistance

Fibers formed from glass compositions of the present invention were madein a laboratory using a single tip bushing set up. To compare withcommercial glass fiber corrosion resistance under the same testingconditions, AR-, C-, ECR- and E-glass fibers were also made using thesame method using cullet.

Glass fiber resistance to corrosion was evaluated in terms of therelative sample percent weight loss after leaching test. Testing wasadministered by boiling a fiber strand at 100° C. for one hour insulfuric acid or sodium hydroxide solutions under various pH conditions.All of the tests were performed by keeping ratio of solution volume tothe sample mass or volume (5,000 m²) constant. 50 ml of the solution andof 1.375 gram (filament diameter—22 μm) were used for each test.Triplicate samples were tested to determine average sample weightlosses. The results of the acid and alkaline corrosion resistancetesting are provided in Table X.

TABLE X Acid and Alkaline Corrosion Resistance Results (% Weight Loss)pH 0 2 12 14 1N 0.1N 0.1N 1N H₂SO₄ H₂SO₄ NaOH NaOH Note E-glass (1) 1.020.19 0.29 1.24 0 B₂O₃ E-glass (2) 1.04 0.00 0.51 0.92 1.3 B₂O₃ E-glass(3) 17.79 0.87 1.62 6.0 B₂O₃ ECR 0.66 0.00 0.13 1.11 0 B₂O₃ + 4 ZnOC-Glass² 0.09 0.13 0.36 7.83 0 B₂O₃ AR-Glass I³ 0.10 0.00 0.00 0.10 17ZrO₂ Ex 10 1.12 0.21 0.84 6.42 Baseline Ex 11 3.58 0.15 0.38 5.60 1%ZrO₂ + 3% TiO₂ Ex 12 4.38 0.21 0.62 2.23 2.9 ZrO₂ + 1.1% TiO₂ Ex 13 4.790.64 0.40 1.01 8% ZrO₂ Ex 12 0.59 0.22 0.26 8.13 baseline Ex 38 1.500.09 0.68 11.02 Ex 18 3.10 Ex 19 0.69 0.66 0.31 8.47 Ex 57 2.20 2.29 Ex58 2.75 3.81 Ex 59 5.35 5.54 Ex 63 1.64 2.89 Ex 67 1.35 3.57 Ex 71 1.193.30 ¹ The average determined from three individual tests and standarddeviation is not greater than 0.1%. ²C-glass (wt %): 66 SiO₂, 5.5 Al₂0₃,10.4 CaO, 3.6 MgO, 0.3 Fe₂O₃, 0.2 K₂O, 12.5 Na₂O, 0.5 F and 0.2 SO₃.³AR-glass (wt %): 57 SiO₂, 3.2 Al₂O₃, 15 ZrO₂, 4.2 CaO, 0.1 MgO, 0.1Fe₂O₃, 0.1 K₂O, 12 Na₂O, 0.5 F and 0.23 SO₃.

III. Mechanical Testing

Tensile strengths of fibers formed from the glass composition of Example37 of the present invention were measured by drawing 10-um diameterfibers from single tip bushing in laboratory. The fibers weresubsequently tested by applying tensile force to the fibers from bothends within the same day of fiber forming. FIG. 9 summarizes Weibullstatistical analysis of the fiber strength with an average of about 3050MPa and standard error of 22.4 MPa for sample size of 57. Except for thetail, the strength fit the single Weibull distribution well suggesting asingle failure mode dominates the fiber failure.

Fiber sonic tensile modulus was measured by drawing 30-um diameterfibers comprising the glass composition of Example 37 of the presentinvention from a single tip bushing in laboratory. The fibers weresubsequently tested by applying dead weight from both ends to measurevelocity of sound traveling inside the fiber. Fiber density was alsomeasured. The elastic modulus was calculated using E=pC² where E, p, andC are modulus, density, and sound velocity, respectively. Fibers of twosets were formed at two different temperatures, the first set at 1000Poise melt viscosity (Low T Forming) and the second set at 50° C. higherthan the first set. (High T Forming) Table XI summarizes the statisticalanalysis of the fiber modulus with an average of about 56.8 GPa and 61.5GPa for low and high forming temperature cases, respectively.

TABLE XI Tensile Modulus Statistics Low T Forming High T Forming Mean(GPa) 56.79 61.47 Std Dev (GPa) 4.41 6.73 Std Err Mean (GPa) 0.99 1.37upper 95% Mean 58.86 64.31 lower 95% Mean 54.73 58.62 Sample Size N 2024 Fiber Diameter (μm) 29.96 ± 0.36  30.17 ± 0.42  Fiber Density (g/cm³)2.356 ± 0.006 2.251 ± 0.028

Desirable characteristics, which can be exhibited by embodiments of thepresent invention, can include, but are not limited to, the provision ofnew glass compositions that utilize glassy minerals; the provision ofnew glass compositions that utilize perlite; the provision of batchcompositions requiring less energy to form melts of glass compositions;the provision of new glass compositions demonstrating significantdifferences in liquidus and forming temperatures; the provision of glassfibers having reduced weights without a concomitant reduction inmechanical properties; and the provision of glass fibers demonstratingdesirable acid and alkaline corrosion resistance properties.

It is to be understood that the present description illustrates aspectsof the invention relevant to a clear understanding of the invention.Certain aspects of the invention that would be apparent to those ofordinary skill in the art and that, therefore, would not facilitate abetter understanding of the invention have not been presented in orderto simplify the present description. Although the present invention hasbeen described in connection with certain embodiments, the presentinvention is not limited to the particular embodiments disclosed, but isintended to cover modifications that are within the spirit and scope ofthe invention, as defined by the appended claims.

That which is claimed:
 1. A glass composition formed from a batchcomposition, the batch composition comprising: at least 10 weightpercent of a glassy mineral, the glassy mineral comprising a combinationof SiO₂ and Al₂O₃ in an amount of at least 80 weight percent; at least 5weight percent of a sodium source.
 2. The glass composition of claim 1,wherein the batch composition comprises at least 10 weight percent of asource of both silicon and aluminum.
 3. The glass composition of claim1, wherein the batch composition comprises at 10 least weight percent ofa source of silicon.
 4. The glass composition of claim 1, wherein thebatch composition comprises at least 10 weight percent of a source ofaluminum.
 5. The glass composition of claim 1, wherein the batchcomposition comprises at least 25 weight percent of the glassy mineral.6. The glass composition of claim 1, wherein the batch compositioncomprises at least 40 weight percent of the glassy mineral.
 7. The glasscomposition of claim 1, wherein the batch composition comprises at least10 weight percent of the sodium source.
 8. The glass composition ofclaim 1, wherein the glassy mineral comprises perlite, pumice ormixtures thereof.
 9. A glass fiber formed from a batch composition, thebatch composition comprising: at least 10 weight percent of a glassymineral, the glassy mineral comprising a combination of SiO₂ and Al₂O₃in an amount of at least 80 weight percent; and at least 5 weightpercent of a sodium source.
 10. The glass fiber of claim 9, wherein thebatch composition comprises at least 10 weight percent of a source ofboth silicon and aluminum.
 11. The glass fiber of claim 9, wherein thebatch composition comprises at least 10 weight percent of a source ofsilicon.
 12. The glass fiber of claim 9, wherein the batch compositioncomprises at least 10 weight percent of a source of aluminum.
 13. Theglass fiber of claim 9, wherein the batch composition comprises at least25 weight percent of the glassy mineral. 14-15. (canceled)
 16. The glassfiber of claim 9, wherein the glassy mineral comprises perlite, pumiceor mixtures thereof.
 17. The glass composition of claim 1, wherein theglass composition comprises: 53-64 weight percent SiO₂; 8-12 weightpercent Al₂O₃; 8.5-18 weight percent alkali oxide component (R₂O); and ametal oxide (RO) component, wherein the metal oxide component is presentin an amount to provide a ratio R₂O/RO ranging from about 0.15 to about1.5.
 18. The glass composition of claim 17, wherein the RO component ispresent in an amount ranging from 7 weight percent to 31 weight percent.19. The glass composition of claim 17, wherein the RO componentcomprises a mixture of Cao and MgO.
 20. The glass composition of claim17, wherein the RO component comprises CaO in an amount ranging from 7to 26 weight percent.
 21. The glass composition of claim 17, wherein theRO component comprises MgO in an amount up to 5 weight percent. 22-26.(canceled)
 27. A method of producing a glass fiber comprising: providinga batch composition comprising at least 10 weight percent of a glassymineral and at least 5 weight percent of a sodium source, the glassymineral comprising a combination of SiO₂ and Al₂O₃ in an amount of atleast 80 weight percent; heating the batch composition to form a melt ofthe glass composition; extruding the molten glass through a bushing toform a glass fiber. 28-32. (canceled)